Azabicyclic phosphonate



United States Patent O ABSTRACT OF THE DISCLOSURE A new class of azabicyclic phosphates, which are useful as insecticides and herbicides, having the general formula:

H i ll II C I 2 N-CCHzSP I CH2 CH2H-CH2 wherein X represents oxygen or sulfur, R represents an alkoxyl group having 1-5 carbon atoms, and R represents an alkoxyl or alkyl group having 1-5 carbon atoms.

The above compounds are prepared by reacting ammonium salts of phosphoric acid monoesters and diesters With N-chloroacetyl 3-azabicyclo [3.2.2] nonane.

BACKGROUND OF THE INVENTION This invention relates to a new class of phosphates useful as insecticides and herbicides and in particular to a new class of azabicyclic phosphates useful as insecticides and herbicides.

The requirements for useful insecticides and acaricidals vary depending upon the kind of application intended. To be successful, an insecticide must be toxic to the insect to be controlled. For some applications, it is desirable that the insecticide be stable and have residual activity; for other applications, it is desirable that its useful life be short. For use by unskilled personnel, it should be relatively non-toxic to mammals; in other cases, particularly where it is to be applied only by skilled personnel, the mammalian toxicity is less of a factor. Of course, where the insecticide is to be applied to the foliage or roots of plants, or to soil in which the plant is' growing, it'must be nonphytotoxic, at least at the insecticidal dosage. The same considerations apply in the case of a herbicide. The herbicide must effectively control the growth of weeds or kill the weeds without harming the plant sought to be protected.

It is one object of the present invention to produce a new class of phosphates useful as insecticides, acaricides, and herbicides.

It is another object of the present invention to produce a new class of N-acetyl 3-azabicyclo [3.2.2] nonane phosphates.

It is a further object of the present invention to provide a process for producing a new class of N-acetyl 3-azabicyclo [3.2.2] nonane phosphates useful as insecticides, acaricides, and herbicides.

SUMMARY OF THE INVENTION The following general structure represents the compounds of the invention:

wherein X represents oxygen or sulfur, R represents an Patented Mar. 17, 1970 ICC alkoxyl group having 1-5 carbon atoms, and R represents an alkoxyl or alkyl group having 1 to 5 carbon atoms.

These compounds are viscous liquids which are soluble in many organic solvents but are essentially insoluble in water. They have outstanding acaricidal activity. Accordingly, they can be used safely and very effectively for combatting eggs and active stages of spider mites in the protection of plants. These compounds can also be used as active toxicants in compositions for the control of a number of insect organisms such as flies, beetles, roaches, cattle grubs, and aphids. Furthermore, the compounds of the present invention are very effective herbicides which may be used to control weeds such as crabgrass, Johnson grass, and wild oats with little or no injury to staple crops such as wheat, cotton, corn, soybean, and ryegrass. More over, the toxic potency of this class of compounds is such so as to permit their effective use as dilute solutions in soaps, sprays, paints, and oils.

DESCRIPTION OF THE PREFERRED EMBODIMENT The synthesis of this class of phosphates may be carried out by reacting ,N-chloroacetyl 3-azabicyclo [3.2.2] nonane with an ammonium salt of a monoester or diester of phosphoric acid as illustrated by the following reaction:

Hz( JH-CH2 wherein X represents oxygen or sulfur, R represents an alkoxyl group containing 1-5 carbon atoms, and R represents an alkoxyl. or alkyl group having 1-5 carbon atoms. The reaction may be carried out in any common inert organic solvent such as acetone, benzene, dimethylformamide or carbon tetrachloride. Approximate stoichiometric amounts of the reactants are used. The reaction mixture is allowed to react with agitation at ambient temperatures of generally 15-35 C. and preferably 2030 C. and at atmospheric pressure although higher pressures may be used. The mixture is allowed to react for 812 hours. After the completion of the reaction, the reaction mixture is filtered and the solvent is removed from the filtrate under reduced pressure. The filtrate is then taken up in a water-immiscible organic solvent, such as methylene chloride, and the resulting solution is washed three times with Water. The organic layer is dried over a drying agent, such as anhydrous magnesium sulfate. After the organic layer has been dried, the organic solvent is removed under reduced pressure to produce a viscous oil residue product.

Preparation of typical compounds of the present invention are described in the following example. The example is intended to be illustrative and exemplary in character, only, is not to be considered as limiting the invention in any way. The reaction conditions can also be modified without departing from the spirit of the invention.

EXAMPLE I To 2.0 g. of N-chloroacetyl 3-azabicyclo [3.2.2] nonane dissolved in 50 ml. of acetone there was added 2.5 g. of ammonium 0,0 diethyl phosphorodithioate in ml. acetone. The mixture was allowed to react overnight at atmospheric pressure and at ambient temperature. After the reaction period was completed, the reaction mixture was filtered andthe acetone was evaporated from the filtrate. The residue was then extracted in methylene chloride, washed three times with water and dried over magnesium sulfate. Removal of the solvent methylene chloride by evaporation under reduced pressure left 3.0 g. of an oil. The residue product is Compound 1 in Table I below.

Table I sets forth typical examples of compounds of the present invention which were prepared in the same manner as the process described in Example I.

In using the compounds of this invention as insecticides, the'undesirable organism may be killed by contacting the insect directly, by contacting the insect through its habitat, or by contacting the insect through its food prior and after ingestion with toxic amounts of the compounds. Standardized tests both non-systemic and systemic were conducted to determine the effectiveness as insecticides and acaricides of the compounds listed in Table I armyworm larvae (SAL) and pea aphid adults (PAA).

TABLE I delivered from a DeVilbiss atomizer nozzle at 20 p.s.i. The approximate volume of spray on the upper surface was 0.19 cc. and the under surface was 0.48 cc. After spraying, the deposits were allowed to dry on the plants and 5 3rd instar larvae were then confined on each plant with 6 inch screen wire spheres. Mortality and feeding records were made 3 days after treatment.

TEST II Non-systemic test for .pea aphid adults (PAA) A solution consisting of 4.8 grams of Compound 1 was mixed in 100 cc. of acetone. The solution was diluted with water sothat the concentration of Compound 1 was 1 oz./ 100 gal.

English broad bean plants were sprayed for 2 seconds on upper surface and 5 seconds on under surface with this solution. Adult female aphids (10 per test) were brushed from infested broad bean plants into 5 inch screen wire hemispheres and sprayed for 5 seconds (approx. 0.6 cc. delivery per second from nozzle). S'pray Analysis Compound Conipound No.

(Hz-CH-CH:

OH: H II N-e-C CH2SP(O C2H5)2 r CHz-r-CH- H:

CH CH-CH 2 o s 001m CH2 ll ll l NCCH2BP r CHz-CH-CH;

CHr-CH-CH:

0 CH2 II II B NC CHQSP (OCgHQg CHPH-CHZ The following non-systemic tests were performed to illustrate the use of the compounds of Table I in controlling insects and acarids. The results of the tests are listed in Table II.

TEST I Non-systemic primary test for Mexican bean beetle larvae (MBBL) A solution consisting of 4.8 gm. of Compound 1 was mixed in 100 cc. of acetone. The solution was diluted with water so that the concentration of Compound 1 was 1 oz./100 gal.

Horticultural (cranberry) bean plants, in 2 /2 inch pots with all foliage removed except one primary leaf, were sprayed with the solution for 2 seconds on the upper surface and 5 seconds on the under surface. The spray'was Calculated Found was applied from a DeVilbissatomizer nozzle at 20 p.s.i., with the aphids 15 inches from nozzle. Following treatment, aphids were caged over previously sprayed plants and mortality records were usually made 3 days later.

TEST III Non-systemic primary test for southern armyworm larvae (SAL) A solution consisting of 4.8 gms. of Compound 1 was mixed in cc. of acetone. The solution was diluted with water so that the concentration of Compound 1 was 4 oz./10O gal.

Horticultural (cranberry) bean plants, in 2 /2 inch pots with all foliage removed except one primary leaf, were sprayed with the solution for 2 seconds on the upper surface and 5 seconds on the under surface. The spray was delivered from a DeVilbiss atomizer nozzle at p.s'.i. The approximate volume of spray on the upper surface was 0.19 cc. and the under surface was 0.48 cc. After spraying, the deposits were allowed to dry on the plants and 5 4th and 5th instar larvae were then confined on each plant with 6 inch screen wire spheres. Mortality and feeding records were made 3 days after treatment.

TEST IV Non-systemic primary test for two-spotted spider mites (TSSM) A solution was prepared of 4.8 gm. of Compound 1 in 100 cc. of acetone. The solution was diluted with water to a concentration of 8 oz./ 100 gal. of Compound 1.

Young horticultural (cranberry) bean plants in 2 /2 inch pots were infested with mites (all stages) one day before treatment. In treating plants the upper surface was sprayed with the solution for two seconds and the lower or under surface was sprayed for five seconds. The spray was delivered from a DeVilbiss atomizer nozzle operated at 20 p.s.i. with the plant about 18" from nozzle. The approximate volume of spray on the upper surface was 0.13 cc. and on the lower surface was 0.32 cc. Following the treatment, the potted plants were placed in irrigated trays in the greenhouse and initial kills of adults were recorded 3 days later. Residual and ovicidal observations were made 78 days after treatment, which allowed ample time for the eggs to hatch under greenhouse conditions. One leaf from each plant was used to make 3-day counts, and the remaining leaf on each plant was used to determine residual and ovicidal activity.

TEST V Non-systemic primary test for house fly adults (HFA) Dry food (6 parts powdered non-fat dry milk, 6 parts granulated sugar and 1 part powdered egg) was mixed with an acetone solution of Compound 1 so that the food contained 0.125% of the compound. The mixture was allowed to dry and then repulverized. Wettable powders are mixed with the dry food with the aid of motar and pestle. The treated food was placed in emergence cages containing 50 fly pupae. Cages containing untreated food were used as checks. Examination of each cage was made periodically for 8 days to determine emergence, condition of flies, and acute toxicity.

Similar tests were performed for Compound 2, the results of which are disclosed with those of Compound 1 in Table II. The compounds of the present invention were very effective insecticides except in the case of the southern armyworm.

TABLE II.-RESULTS OF NON-SYSTEMIC PRIMARY TESTS Percent Mortality MBBL, PAA, SAL, 'ISSM, HFA, Test I, Test II, Test III, Test IV, Test V, Compound 1 oz 1 oz./ 4 oz./ 8 oz./ Percent N0. 100 gal 100 gal. 100 gal. 100 gal. 9-day kill The same compounds were then put through systemic primary tests. The systemic primary tests were conducted for MBBL, PAA, SAL, and TSSM.

TEST VI Systemic primary test for mexican bean beetle larvae (MBBL) container. Aluminum foil was fitted over the top of the container and around the stem of the plants to lessen possible fumigant effects of the compounds tested. The insects were placed on the plants within 24 hours after treatment .and the mortality records were made 3 days later.

TEST VII Systemic primary test for pea aphid adults (PAA) A standard acetone solution containing 4.8 gms. of Compound 1 per cc. of acetone was diluted with water to 4 oz./100 gals. H O. After dilution, 100 cc. of the solution were placed in glass jars, along with the test plants (young English broad bean plants) whose roots have been washed free of soil. The roots of the test plants were in contact with the bottom of the container. Aluminum foil was fitted over the top of the container and around the stem of the plant to lessen possible fumigant effects of the compounds tested. The insects were placed on the plants within 24 hours after treatment and the mortality records were made 3 days later.

TEST VIII Systemic primary test for southern armyworm larvae (SAL) A standard acetone solution containing 4.8 gms. of Compound 1 per 100 cc. of acetone was diluted with water to 4 oz./100 gals. of H 0. After dilution, 100 cc. of the solution were placed in glass jars, along with the test plants (young horticultural (cranberry) bean plants) whose roots have been washed free of soil. The roots of the test plants were in contact with the bottom of the container. Aluminum foil was fitted over the top of the container and around the stem of the plant to lessen possible fumigant effects of the compounds tested. The insects were placed on the plants within 24 hours after treatment and the mortality records were made 3 days later.

TEST IX Systemic primary test for two-spotted spider mites (T SSM) A standard acetone solution containing 4.8 grams of Compound 1 per 100 cc. of acetone was diluted with water to 4 oz./100 gals. of H 0. After dilution, 100 cc. of the solution were placed in glass jars, along with the test plants (young horticultural (cranberry) bean plants) whose roots had been Washed free of soil. The roots of the test plants were in contact with the bottom of the container. Aluminum foil was fitted over the top of the container and around the stem of the plant to lessen fumigant effects of the compounds tested. The insects were placed on the plants within 24 hours after treatment and the mortality records were made 3 days later. The ovicidal and residual data was recorded 8 days after the treatment.

The results of Tests VIIX for Compounds 1 and 2 are listed in Table III. It is noted that the compounds have good systemic activity against insects and acarids.

TABLE III.RESULTS OF SYSTEMIC PRIMARY TESTS [Percent Mortality] Used in dil. of 4 oz./l00 gals. H2O

Test VI, Test VII, Test VIII, Test IX, MBBL PAA SAL TSSM Compound No.:

7 4 8 remaining harmless to the desirable plant such as corn, placed in the greenhouse, watered by sub-irrigation and cotton, etc. held for a 16 day observation period after which they TEST X were rated.

Post-emergence tests Primary and secondary emergence tests of herbicides Erght to 10 days after seeding, two equivalent flats were Plammg crop specles (hsted below) treated with each candidate chemical at a rate equivalent and test d Specles w Planted metal flats to 16 pounds of active chemical per acre. Application and (12 X 81/2 X Crop specles were Planted m smgle OWS post application handling was the same as for pre-emerof 10 com Seeds, 40 Wheat Seeds 15 cottfm and gence tests, except a 10 to 12 day observation period 15 soybean seeds per fiat, and covered with 1% inches 10 was used of soil. The soil used was a composted greenhouse pot- (B) SECONDARY TESTS ting soil consisting of one-third mixed clay and sand, onethird spent mushroom soil, and one-third peat moss. All FIB-emergence tests $0'i1 eemponellte were thoroughly miXed- T P of the Application of eight and four pounds active chemical sorl was 6.8 to 7.2. Weed species were uniformly broad- 15 per acre was d as i primary p e-emergence tests. cast-seeled at the rate of one teaspoonful of ryegrass, p li i h dli was th ame,

and teaspoonful of rape, per fiat, and covered with inch of soil. Three weed species, crabgrass, Johnson grass, Post'emergence tests and wild oats were planted separately in three inch square Application of eight and four pounds active chemical pots. Two pots of each species were planted. per acre was made as in primary post-emergence tests.

Crop species.--Corn, Zea mays, Hybrid US 13; wheat, The effect of the herbicide on the crops was evaluated T riticum vulgare, variety thorne; cotton, Gossypium hirsuand noted in terms of the injury rating index. This intum, variety Delta Pine Lane Fox, No. 20; and soybean, dex was based on scale of O to 10 as follows: 0=no ap- Soja wax, variety Wilson. parent injury; 1, 2, 3=sl=ight injury; 4, 5, 6=moderate in- Wccd species.Annual ryegrass, Lolium multiflorum; jury; 7, 8, 9= ev injury (plants ill di 10= 1 nt rape, Brassica napus; crabgrass, Digitaria sanguinalis; were dead. An injury rating of 3 was the maximum toler- Iohnson grass, Sorghum halepense; and wild oats, Uvuable on crops, and a rating of 7 was the minimum tolerable larz'a sissifolia. on weed plants.

Spray equipment 0perati0n.The spray equipment in- The results of the herbicidal tests for Compounds 1, 2,

cluded an endless flexible steel conveyer belt 2 feet wide 3, and 4 in terms of injury ratings are listed in Table and 12 feet long. The speed of the belt was varied by use IV. 1

TABLE IV.-RESULTS OF PRE-EMERGENCE AND POST-EMERGENCE HERBICIDAL TESTS Compound 1 Compound 2 Compound 3 Compound 4 Amount of Compound Pre- Post- Pre- Post- Pre- Post- Pre- Post and Type of Plant emergence emergence emergence emergence emergence emergence emergence emergence libs/acre 16 8 8 4 Corn, IR 0 2 Cotton, IR- 0 0 Wheat, IR- 6 4 Soybeans, I 0 6 Ryegrass, IR 5 9 Rape, IR 2 4 Crabgrass, IR 9. 9 9

Johnson grass, IR 10 9 Wild oats, IR 9 4 1 100% active ingredient applied in 80 gal. acetone/acre. IR=Injury rating, 0-10; O=n0 injury, 10=complete kill.

of a variable-speed automatic transmission, powered by a H.P. explosion-proof electric motor, a speedometer As is seen from Table IV, in the case of Compound 1 being attached to the belt drive. in the pre-emergence tests, there was poor weed control The equipment further included a spray boom with nozwith moderate injury to the wheat and no injury to the zles, spray mixture reservoir, and accompanying lines for other crops. There was excellent control of crabgrass,

spray mixture and pressure supply. Air was used to sup- Johnson grass and wild oats. The post-emergence tests reply pressure at 30 psi. sulted in moderate injury to broadleaf plants, light injury The seeded flats were placed on the conveyer belt and to corn and no injury to wheat or grass.

carried beneath the spray nozzles at a speed of 1.5 m.p.h. III the Case f C p ill the p ergen t st With a No. 730,154 flat-fan type nozzle for spraying, each there was fair grass control, light broadleaf d C011- flat received a volum of spray equal to 80 gallons of trol, but severe injury'on wheat and corn. There was no spray mixture per acre. Immediately after spraying, the injury to the cotton and soybeans. Furthermore, there test flats were placed in aluminum trays. Water was added was good crabgrass control but Johnson grass and wild to the trays and allowed to remain until the Surface of oats were not effected by the compound. In the post-emerthe soil in th flat was uniformly moist (at field capacity), gence tests, there was light to moderate herbicidal injury After irrigation the 'water was drained from the trays. on all plants except in the case of rape where there was Additional sub irrigation was given, as needed, to main- Severe inj rytain moisture during the test period. No surface irrigation In the case of Compound 3, in the pre-emergence tests, wa applied, there was excellent grass control and good broadleaf weed (A) PRIMARY TESTS control with light crop injury. Furthermore, there was excellent crabgrass control and good Johnson grass control emergence tests with nocfiect on the wild oats. In the post-emergence Within one day after seeding, two flats were treated tests, there was severe injury to rape with moderate inwith each candidate chemical at a rate equivalent to 16 jury to other plants. pounds of active chemical per acre. Application was made In the case of Compound 4, in the pre-emergence tests,

y dissolvi g the compound in acetone. Treated flats were there was excellent grass control and good broadleaf weed 9 control with light to severe crop injury. There was fair crabgrass control with no effect on Johnson grass or Wild oats. The post-emergence tests results indicated severe injury to rape and soybeans With moderate injury to the other crops.

What is claimed is: 1. A compound having the formula:

CH2-(|3H-CH2 0 CH2 H 10 References Cited UNITED STATES PATENTS 3,347,850 10/1967 Baker et a1 260-239 5 FOREIGN PATENTS 1,323,949 3/ 1963 France.

1,355,070 2/1964 France.

1,193,953 6/1965 Germany.

10 ALTON D. ROLLINS, Primary Examiner US. Cl. X.R. 

